Esters of phosphorus acids



'l RENE urureo sures nsreas or rnosrnorws ACIDS Lucas P. Kyrides, Webster Groves, Mo., as signor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application May 26,1938,

' Serial No. 210,157

6 Claims. (01. 260-461 This invention relates to new chemical comremoval of HCl. It will be found that the phospounds and more particularly to new estersof phite is obtained in a substantially pure condi- Dhosphorus acids. tion, there being present only a very smallpro- The principal object of this invention is the portion of hexyl phenol, which, for most purprovision of novel and valuable liquid esters poses, is entirely unobjectionable. This alter- 5 of phosphorus acids and hexyl phenols. native method obviates the purification step out- It has been found that liquid mixtures of tri lined above and may be employed where 'a (hexylphenyl) phosphites may be obtained in technically.pureproduct is not required. substantially theoretical yields by reacting an a In an analogous manner, an isomeric mixture 10 isomeric mixture of hexyl phenols with, a subof hexyl phenols may be used to prepare tri stantially theoretical quantity of phosphorus .(hexylph nyl) phosphate y i With D trichloride. For many purposes a liquid mixture phorus oxychloride. If desired, any of the cataof such phosphites is peculiarly suited for use lysts customarily employed for such reactions in the industrial arts. may be utilized. Alternatively, one may use the A convenient method which may be utilized anhydrous sodium salt of the phenol and POCls, 15 for the preparation of an isomeric mixture of which are p e y allowed 130 react in an hexyl phenols which is eminently suitable for inert medium. use in this process is as follows. A commercial One hundred and fifty parts of phosphorus mixture of hexanes having a boiling range of oxy l r are w y added to fiv nd an 65-70 o. is chlorinated to the monochloro dethirty-five pa ts of ed hexyl phenols eontaim rivativcs. The mixture of hexyl chlorides is five pa O a aluminum Chloride catalyst then reacted with phenol to form a mixture pre- 7 at 95 C. After the addition is complete, the, dominately of the para alkyl derivatives but temperature is slowly raised to 150 C. and maincontaining some ortho. This reaction may be tained for several hours, after which time a carried out without a catalyst or in the presva uum may ap d to m te the a t n- 25 ence of any of those commonly employed for The ester, a viscous oily liquid, may be recovered such purposes such as zinc chloride, aluminum in the S me a ne s t Corresponding D chloride, sulfuric acid or the like. The result- Dhite p p d abOVeing mixture of hexyl phenols is isolated and is e ed tri y pheny DhOSDhitES and suitable for use in the instant invention. the correspond mixed tri y p y 'D 30 As a specific example, 130 parts of phosphorus ,phates have been foundto be valuable adjuvant trichloride are slowly added to 535 parts of adapted to be added to oils and eas mixed hexyl phenols at 95 C. After the add} Recent advances in the automotive engine detion is complete, the temperature is slowly raised n v tended toward higher bearing pr sto 150 0. and maintained there for several hours. s, hi r speeds of rotation d higher n- 35 To complete the reaction a vacuum may be apgille pe esc C es have 06- plied. The ester may be recovered from th casioned a departure from the usual metals emreaction mass by dilution with an organic solp ye for bearings and adoption of harder mavent such as benzene and extraction of the free s, c as a u -S ver, cadmium-nickel,

40 phenoland acid esters with NaOH solution. The pp alloys the likeconelllrently 40 benzene is then removed by heating under a with this change to the new bearing materials vacuum, the removal being accelerated if dea demand has arisen for oils having a higher sired by the use of an entraining liquid such as viscosity index, i. e., a smaller change in viscosity i a stream of dry nitrogen. The tri (hexylphenyl) with change in temperature. This demand. has

phosphite is obtained as an oily, viscous liquid been met by improved methods of refining which 5 at ordinary temperatures. have made possible a greatly improved product.

It is preferable to use a small excess of phenol, However, these improved oils have been found g 2% to 5%, to insure complete conversion to be definitely corrosive toward the new bear- Of the C 3 t e estering materials which, although they are harder For certain purposes it may be desirable to than the older type, such as babbitt, are much 50 prepare the tri (hexylphenyl) phosphites by the more susceptible to such attack. use of theoretical quantities of reactants. Under It has been found that when the compounds these circumstances the reaction is forced pracforming the subject matter of this invention are tically to completion by the use of a vacuum admixed with oils or greases in quantities as 5 and preferably an entraining gas to facilitate the small as 5 of 1% or even less the tendency to corrode the newer type bearings otherwise shown by such oil or grease is substantially completely prevented. In addition, it has been found that the admixture of these compounds with oils and greases increases the film strength of the resulting product and reduces the amount of wear normally occurring when the bearing is in use over what is encountered when the oil or grease alone is used. There are also indications that the amount of carbon formed is reduced. In many cases it may be desirable to incorporate the phosphites or phosphates, in quantities as large as 1% or more, with certain oils. In fact, 4% or 5% may be employed where the object is to increase the film strength, although much smaller amounts will prevent corrosion.

When the compounds of this invention are employed for the purposes outlined, it has been found that they do not impart an objectionable odor such as carbolic acid to the product. Many of the derivatives of phenols previously employed for analogous purposes are subject to this objection and the widespread complaints of customers who objected to such an odor have severely limited their application.

Moreover, it has been found that the tri (hexylphenyl) phosphates prepared above are valuable plasticizers and high boiling solvents. Although they are especially valuable for use with nitrocellulose, they may also be employed with other cellulose esters such as cellulose acetate, and

with other plastics such as vinyl resins and the like. For most purposes it will be found that a mixture containing about 25% of the plasticizer based on the weight of the plastic is satisfactory.

In addition it will be noted that the compositions described herein are liquids whereas such commercial materials as tertiary butyl phenol, although of lower molecular weight are solid at normal temperatures. The fact that these materials are liquids renders them peculiarly suitable for use as high boiling solvents, plasticizers, adjuvants for oils and greases and the like.

What is claimed is:

1. An isomeric mixture of tri (hexylphenyl) phosphites which is liquid at ordinary temperatures.

2. An isomeric mixture of tri (hexylphenyl) phosphates which is liquid at ordinary tempera tures.

3. The liquid ester reaction product of P013 and hexy1-substituted phenol.

4. The liquid ester reaction product of POCls and hexyl-substituted phenol.

5. An isomeric mixture selected from the group consisting of tri (hexylphenyl) phosphites and tri (hexylphenyl) phosphates, which mixture is liquid at ordinary temperatures.

6. The liquid ester reaction product of a member of a group consisting of P013 and P0013, and hexyl substituted phenol.

LUCAS P. KYRAIDES. 

